Process of dyeing and printing of textile goods and other materials adapted to be impregnated



Patented Mar. 9, 1926.

UNITED STATES PATENT" OFFICE.

MARCEL BADER, OF MULHOUSE, FRANCE, THEODORE LOMBARD, OF xBASEL, SWITZER- LAND, CHARLES SUNDER, 0F MULHOUSE, FRANCE, AND CHARLES VAUCI'IER, 0F BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY DURAND & HUGUENIN S. A., OF

BASEL, SWITZERLAND.

PROCESS OF DYEING AND PRINTING OF TEXTILE GOODS AND OTHER MATERIALS ADAPTED TO BE IMPREGNATED.

No Drawing.

To all whom it may concern Be it known that we, MARCEL BADER, a citizen of the French Republic, and resident of Mulhouse, Alsatia, France, THE'oDoRE LOMBARD, a citizen of the Swiss Republic, and resident of Basel, Switzerland, CHARLES SUNDER, a citizen of the French Republic, and resident of Mulhouse, Alsatia, France, and CHARLES VAUoHER, a citizen of the Swiss Republic, and resident of Basel, Switzerland, have invented a new and useful Process of Dyeing and Printing of Textile Goods and Other Materials Adapted to be Impregnated, of which the following is a full, clear, and exact specification.

Dyeings produced with vat-dyestuffs, that is to say by introducing into or depositing upon the goods insoluble dyes as pigments, are rightly accounted, together with certain other developed pigment dyeings, like aniline black and the so-called ice colors, as the fastest dyeings.

Indigo dyeing is the commonest example of this form of the art. Long experience has shown that in the art of indigo dyeing strict conditions must be observed in detail: this is the case, for example, in the preparation of the stock vat, in which operation, apart from the quality of the indigo which is all important in respect of the method of vatting and may modify the operation in many ways, the management of the vat itself requires exact supervision in regard to its alkali coITtent and its dyestuff concentration. Management of old vats is particularly difficult but unavoidable, since indigo dyeing is possible only in voluminous vats and the loss of indigo would be excessive if the vats were frequently renewed.

At the present time the hydrosulfite-alkali vat is the most perfect; however, it gives varying results and its yield or output changes from place to place. Over-reduct1on is apt to cause loss of indigo in these vats. The hydrosulfite suffers loss of reducing power in contact with the air, so that these vats require careful supervision.

If a deep color is required, which is fast and which penetrates through the fabric, several passages through one and the same Application filed July 24, 1923. Serial No. 653,567.

vat or through several vats in series are necessary, and between the passages there must be exposure to air; or the dyeing to the desired tint must be obtained by repeated immersion in an immersion vat. In these operations the fibre takes up a part of the sodium-indigo-white which is well retrained and later is precipitated in the fibre in the greening operation. Another part of the sodium indigo Vat remains in the wetting liquor and is deposited superficially as indigo which adheres only loosely to the fibre. This portion constitutes a loss which is by no means negligible. In order to obtain uniform dyeings penetrating the fabric throughout, it is indispensably necessary in vat dyeing to use a suitably prepared fibre so that it can easily be wetted.

lVhereas cotton can be dyed without in jury in various vats, wool and silk must be dyed in caustic alkali and ammoniac-al vats with particular care.

In spite of the numerous difficulties, the indigo vat has hitherto reigned supreme because there has not been found any complete substitute, and because indigo dyeing is generally esteemed as a pure blue which is not too costly and lends itself to an improvement by illumination effects either by reserve printing or discharge printing.

Direct indigo-printing is not an easy operation. The utilization of the indigo present in the printing color leaves much to be desired and also the tints produced are liable to be much damaged by the alkali present in the printing color: this alkali is troublesome in many other respects (simultaneous printing of other colors, mercerization of the fabric, supporting band and the like). Other vat dyestuffs are more easily printed but the preparation of the printing color and the fixing of the dye by steam offer difficulties. Furthermore, in contrast with the dyeing methods, the yield or output of the dyestufl leaves much to be desired.

Some vat dyestuffs other than indigo are used for light tints by a padding process. The operation is difiicult, however, when uniform tints and equal dyeing are desired. For dark tints most vat dyestuffs are used i with the so-called submerged jigger, in

which case the edges and the center of the fabric are equally dyed; moreover, the bathis not completely exhausted in this operation.

\ ever, have not had any practical result.

For example, the following methods have been put forward 1. The process of A. Baeyer using orthonitrophcnylpropiolic acid, which has been proposed by the Badische Anilin & Soda Fabrik for indigo printing. The compound is printed with alkalies in presence of a reducing 'agent and then developed to indigo on the fibre. During the development, however, a part becomes isatin, causing loss and rendering the process uncommercial.

2. The process of A. Baeyer using orthonitrophenyl lactic-acid-methyl-ketone, commonly known as Kalles indigo salt T-process, in which the bisulfitc compound and the aforesaid ketone is printed and developed to indigo on the fibre by a hot caustic soda bath of 12-20 Baum specific gravity. The defects of the process are the poor solubility of the compound in water, the poor yield in indigo, the relatively high price and the strong mercerizing effect on ,the cotton.

3. The dehydroindigo-process of L. Kalb, in which the water-soluble bisulfite compounds of dehydro-indigo and its analogues are brought on to the fibre by padding or printing and developed to indigoid dyestuffs by agencies which have not an oxidizing action, such as passage through acid and alkali or exposure to light or heat.

This rocess has not come into practice because oi defective and varying yields of indigo and like dyestuffs.

4. The indophor (indoxyl-carboxylic acid) process of Badische Anilin 8: Soda-Fabrik:.

the compound is printed on the fabric and indigo is developed by passage through an acidified solution of ferric chloride; the ease with which the compound decomposes and the poor yield are against the success of the rocess.

Other attempts relate to preparations which are soluble only in organic solvents and therefore are without practical result.

It will be seen that all the propositions are limited to indigo with the exception of of Kalb, whiclrextends to halogenized 1n lgo.

'A new mode of producing indigo and other vat dyeings is afforded by the use of the water-soluble ester-like derivatives of leuco-vat dyestuffs (ester-salts) which are described in the U. S. Patent No.

I 1,448,251/ In substance or in dissolved constable to air. Their solutions can be handled, stored and heated without damage. They are insensitive to alkalies but not to mineral acids at high temperatures, being then more or less easily decomposed.

These compounds exhibit the surprising property that they are converted easily, guickly and giuantitatively into their funamental vat yestufi's (indigo, halogenized indigo, thio-indigo or the like) directly they are treatedin aqueous, preferably acidified, solution, with oxidizing agents, even of a gentle kind. One thus becomes possessed of an essentially simple process for producing all intensities of color in dyeing throughout or by local printing. The operation may be as follows i The yarn, thread, fabric or the like, is impregnated with a solution of the compound in question which needs no addition. It is then dried in order to avoid loss and developed in a bath of ferric chloride or acidified chromate or the like, at ordinary or raised temperature. The compounds have for the most part no affinity for the goods to be dyed but are perfectly introduced also into the crude material and there precipitated in very fine state of subdivision by the oxidation. It is a fact that indigo produced in this manner gives rise to dyeings which are faster and more uniform than is the case in the ordinary dyeing processes, however carefully these may be conducted. Even the thickest materials may be dyed throughout by this process in a single passage through .the bath, which cannot be the case with the ordinary vat. Since the compounds in question are neutral bodies, any kind of fibre (cotton, raw-cotton, dead-cotton, cellulose, wool, silk, mixed textile fibres) following indisputable technical advance and effects.

It yields at onceuniform and certain dyeing which is not the case with indigo vats hitherto used.

The indigo vat processes of the present day require much and costly apparatus. This means that the vat dye-house is applicable only on a large scale. The process of this invention, however, may be practised in the smallest scale with a production of uniform dyeings and is therefore applicable with much simpler mechanical devices. Even the smallest dyehouse may produce at any time a fast indigo dyeing by this new process.

By the process of the invention there is obtained an almost theoretical use of dyestuif since the solutions can-be fully exhausted. There is a further advantage that the solutions of the bodies here used will stuffs of other classes can be printed, to-

gether with those in question, provided that they will withstand the subsequent oxidation treatment; this is not possible with indigo.

The developed uni-dyeings can be discharged, so far as the dyestuffs-producing them are capable of being discharged by the usual methods.

The padding and printing colors may carry an additionof an oxidizing agent. This latter must be inefficaeious in neutral or in Weak alkaline medium, but it must be reacting in an acid medium. Such color pastes containing the ester-salt and an oxidizing agent are durable for some time. The goods prepared or preliminarily printed with these colors are dried and afterwards passed through a bath of diluted mineral acid, sulfuric acid or oxalic acid. The oxidizing agent becoming efficacious and the dyeing, for instance indigo, is rapidly developed.

' Oxidizing agents very suitable for this pur-- pose are chromates or nitrites.

In many cases, particularly for dyeing wool, silk, leather, in general the animal fibres, it is ad antageous to execute the padding operation in the bath of ester-salt and oxidizing agent as well as also the subsequent treatment withacid at a raised tem perature. 1 I

The treatment of the padded fibre with acid for developing the dyeing, may also be carried out by subjecting the fibre to the action of the vapour of a volatile acid such as acetic acid or formic acid.

It has further been-observed that in dyeing operation the ester-salts have an affinity by adding an acid to the dye-bath.

Dyeing gives good uniform results by beginning with a bath, feebly acid, containing for instance an organic acid or an acid salt (bisulfate oii sodium or sulfate of aluminium), and by finishing with a bath containing a mineral acid, complete exhaustion is effected,

It is possible by fibres like acid coloring matters.

. The products are absorbed by the goods in an uncolored form. After'the fixation of the bodies on the fibre, the color is developed by means of a suitable oxidizing agent.

This modification of the dyeing process offers new great advantages. The same fast colors are obtained as with the corresponding vat-dyestuffs, but by a better process which is less injurious to the fibre than the alkaline vat dyeing method. Because the dye-bath is completely exhausted, the dyeing can be exactly adjusted. The oxidizing agent can be added to the same bath, in a like manner as in the chromating process of an acid dye. I

The penetration of the fibre and the fastness to rubbing are better than by the aforesaid padding process.

New methods of illumination are now possible. If a white effect is to be produced on goods preliminarily treated with estersalt and oxidizing agent, a thickened hydrosulfite body is printed. In the subsequent passage through acid the parts thus printed remain uncolored.

For the hydrosulfite preparation other suitable reducing agents such as sodium sulfite or sodium thio'sulfate may be wholly or in part substituted; generally any chemical substance may be substituted which is suitable for neutralizing the action of the oxidizing agent applied.

If colored effects are desired, there is added to the White discharge a vat dyestuff and 'the goods are steamed and developed by passage through acid and washed. One can thus obtain in particularly simple manner a "vat dyestufl illumination on a vat ground, a long-sought, fast, variegated effect.

Besides vat dyestuffs, there may be added to the white reserve:

(a) Basic dyestuffs with tannin or one of its substitutes.

(b) Mordant dyestuffs,

(c) Dyestuffs which can be fixed by means of albumen,

(d) Dyestuffs capable of being developed, such. as n'itrosamine red dyestuffs, by the use of sodium-thio-sulfate as a reserve agent,

(6) In general any dyestuffs which can be fixed and withstand the reserve agent.

Besides this reserve process, discharge processes are also possible; for instance printing a rongalite-discharge-salt-W-discharge, which is mixed with the dihydroindigo-ester-salt, on a thio-indigo ground. By steaming, the ground is discharged but the indigo derivative remains uninjured and may be developed to blue in a subsequent warm ferric chloride bath. A similarcolour discharge may be producedv on a diamine' v dyestuff ground.

,this means reapply-this new ester-salts for W001 and' other animal Nitrosamine red dyestufis and ester-salt dyestuffs 'may be printed withv oxidizing agents side by side on a white groundand developed by passage through acids (bluered effect),

- light of a mercury vapour lamp).

Many new reserve discharge and conversion effects are conceivable.

It will be seen from the foregoing that by the present invention the vat and its supervision are eliminated.

The dyeings obtained have the same valuable properties as those obtained by the processes hitherto used.

Moreover, the process permits the dyeing of various materials at any stage of their preparation.

By'manifold combinations effects of the most various kind can be obtained.

All this proves the aforesaid technical importance attaching to the present invention.

There is still to be noted the property of the dihydro-thio-indigo derivative (in smaller degree also the other derivatives) that its ester-saltis developed to dyestutf in a short time by exposure to light (sunlight or the This property suggests a photochemical application of the body.

What we claim is v 1. A process for dyeing and printing with vat-dyestuffs, consisting in applying to the goods a water-soluble ester-like derivative of a vat-dyestuif and then developing the dyeing thereon by reforming the dyestuff by action of a suitable oxidizing agent.

2. -A process for-dyeing and printing with vat-dyestufi's, consisting in applying to the goods a Water-soluble ester-like derivative of a vat-dyestufi with an oxidizing agent and then passing the goods through acid in order to develop the dyestufi'.

3. A process or dyeing and printing with vat-dyestufls, consisting in applying to the goods a water-soluble ester-like derivative of a vat-dyestufl with an oxidizing agent,

printing thereon a suitable agent capable of neutralizing the effect of the oxidizing agent, and then passing through acid for the purpose of colored ground.

4. A process for dyeing and printing with producing a white effect on a ,of a vat-dyestuff with an oxidizing agent,

printing thereon a sodium-thiosulfate paste and then passing through acid, for the pur pose specified.

5. A process for dyeing and printing with Vat-dyestuffs, consisting in applying to the goods a Water-soluble ester-like derivative of a vat-dyestuif With an oxidizing agent, printing thereon a suitable agent for neutralizing the efiect of the oxidizing agent, in combination with a fixalole dyestufi' capable of withstanding the reserving agent, steaming and passing through acid, for the purpose of producing a colored effect on a colored ground.

(3. A process for dyeing and printing with vat-dyestuffs, consisting in printing on a colored gnound a water-soluble ester-like derivative of a vat-dyestufi, in combination with a suitable discharging agent, steaming thereupon to produce a discharge effect and developing by oxidation the vat-dyestufl? resulting from the unchanged ester-like derivative.

7. A process for. dyeing and printing with vat-dyestuffs, particularly on animal fibres, consisting in applying to the goods a Watersoluble ester-like derivative of a vat-dyestufi' and in developing by means of an oxidizing action the color thereon at a raised ten1- perature. v

8. A process for dyeing with vat-dyestuffs on animal fibres, consisting in applying a water-soluble ester-like derlvative of a vatdyestufl' from a feebly acid bath to the goods at a raised temperature and then developing the color thereon by means of a suitable oxidizing agent. i v

In Witness whereof we have hereunto signed our names this 6th day of July 1923.

MARCEL BADER. THEODORE LOMBARD. CHARLES SUNDER.

, CHARLES VAuoHER. 

